The development of efficient and inexpensive catalysts capable of solar-to-fuel energy conversion is vital for mitigating the adverse effects of carbon-based fuels on the environment and meeting the rising global energy demand. Heterogenization of molecular catalysts onto electrodes is an attractive strategy to combine the advantageous properties of homogeneous and heterogeneous catalysis. MOFs have emerged as a promising class of materials; however, their insulating nature has limited their application as electrocatalysts. We have demonstrated the successful integration of metal dithiolene units into one and two-dimensional frameworks by using dinucleating and trinucleating thiolate-based ligand scaffolds. The developed metal dithiolene frameworks display remarkable activity for the electrocatalytic conversion of water into hydrogen and electrical conductivity that is switchable from semiconducting to metallic. We expect the design principles discovered in these studies to have a profound impact towards the development of advanced materials and sustainable technologies.